EP0142467A1 - Polymer compounds containing piperidyl groups and their use as stabilisers in synthetic polymers - Google Patents

Polymer compounds containing piperidyl groups and their use as stabilisers in synthetic polymers Download PDF

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EP0142467A1
EP0142467A1 EP84810455A EP84810455A EP0142467A1 EP 0142467 A1 EP0142467 A1 EP 0142467A1 EP 84810455 A EP84810455 A EP 84810455A EP 84810455 A EP84810455 A EP 84810455A EP 0142467 A1 EP0142467 A1 EP 0142467A1
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formula
group
compounds
butyl
tert
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EP0142467B1 (en
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Giuseppe Dr. Cantatore
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Novartis AG
Ciba Geigy SpA
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Ciba Geigy AG
Ciba Geigy SpA
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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D401/00—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom
    • C07D401/14—Heterocyclic compounds containing two or more hetero rings, having nitrogen atoms as the only ring hetero atoms, at least one ring being a six-membered ring with only one nitrogen atom containing three or more hetero rings
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D471/00—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00
    • C07D471/02—Heterocyclic compounds containing nitrogen atoms as the only ring hetero atoms in the condensed system, at least one ring being a six-membered ring with one nitrogen atom, not provided for by groups C07D451/00 - C07D463/00 in which the condensed system contains two hetero rings
    • C07D471/10—Spiro-condensed systems
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/16—Nitrogen-containing compounds
    • C08K5/34—Heterocyclic compounds having nitrogen in the ring
    • C08K5/3467—Heterocyclic compounds having nitrogen in the ring having more than two nitrogen atoms in the ring
    • C08K5/3477—Six-membered rings
    • C08K5/3492—Triazines
    • C08K5/34926—Triazines also containing heterocyclic groups other than triazine groups

Definitions

  • the present invention relates to new piperidyl radical-containing polymeric compounds which can be used as stabilizers for synthetic polymers against light-induced, thermal or oxidative degradation.
  • the present invention relates to compounds of the formula I. wherein R 1 and R 2 are independently hydrogen, C 1 -C 18 alkyl, by hydroxy, C 1 -C 18 alkoxy or C 2 -C 18 dialkylamino-substituted C 2 - C 12 alkyl, C 3 - C 18 alkenyl, C 5 -C 18 cycloalkyl, C 6 -C 18 aryl, C 7 -C 18 aralkyl or a group of formula II mean, wherein R 6 is hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkenyl or alkynyl, C 7 -C 12 aralkyl or C 1 -C 12 acyl, or R 1 and R 2 together with the nitrogen atom on the they are bonded to form a heterocyclic radical selected from the group consisting of pyrrolidin-1-yl, piperidin-1-yl, hexahydroazepin-1-yl, morpholin
  • R 1 and R 2 have the meaning given above, a is a number between 0.2 and 1 and b is a number between zero and 0.8, the compounds of the formula I having an average molecular weight Mn between 1,000 and Have 20,000.
  • R 1 and R 2 independently of one another are hydrogen, C 1 -C 12 alkyl, C 2 -C 6 alkyl substituted by C 1 -C 12 alkoxy, C 3 - C 6 alkenyl, C 6 -C 10 cycloalkyl or a group of the formula II in which R 6 is hydrogen, methyl, allyl, benzyl or acetyl, or R 1 and R 2 together with the nitrogen atom to which they are attached pyrrolidin-l-yl, piperidine Form 1-yl, hexahydroazepin-1-yl or morpholin-4-yl, R 3 and R 5 are a group of the formula III and R 5 can additionally be a group of the formula VII, R 7 is hydrogen, methyl or ethyl, YC 2 -C 6 alkylene, but-2-ene-1,4-diyl or xylylene, R 4 is C 2 -C 12 diac
  • Preferred compounds of the formula I are those in which R 1 and R 2 independently of one another are C 1 -C 8 alkyl, cyclohexyl, 2,2,6,6-tetramethylpiperidin-4-yl or 1,2,2,6,6-pentamethylpiperidine 4-yl, R 3 and R 5 are a group of the formula III and R 5 can additionally be a group of the formula VII, R 7 is hydrogen or methyl, Y is but-2-ene-1,4-diyl or xylylene , a is the number 1 and b is zero, the compounds of the formula I having an average molecular weight Mn between 1,500 and 6,000.
  • the compounds of the formula I are prepared by reacting a compound of the formula IX with one of the compounds of the formulas XI, XII, XIII or XIV and optionally XV in an approximately stoichiometric ratio.
  • reaction can be carried out without or with an inert organic solvent, in the presence of an organic or inorganic base if A 1 , A 2 , A 3 and A 4 are Cl, or a transesterification catalyst if A 1 , A 2 , A 3 and A 4 are alkoxy.
  • Suitable solvents are e.g. Benzene, toluene, xylene, ethylbenzene, trimethylbenzene, tetralin, decalin, octane, decane, mixtures of aliphatic hydrocarbons with a boiling point between 100 and 200 ° C, dioxane, dibutyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, N, N-dimethylformamide, N, N-dimethalacetamide, N-methylpyrrolidone and dimethyl sulfoxide.
  • a 1 , A 2 , A3 and A4 are alkoxy
  • the polycondensation can at temperatures between 80 and 280 ° C, preferably between 100 and 200 ° C in a molar ratio compound of formula IX + compound of formula X: compound of formula XI, XII, XIII or XIV + compound of formula XV between 1, 3: 1 and 1: 1.3, preferably between 1.2: 1 and 1: 1.2.
  • the different starting materials can be implemented simultaneously or in succession.
  • the compounds of formula IX can be obtained analogously to known processes, starting from cyanuric chloride.
  • the dichlorotriazines or dialkoxytriazines obtained can be used directly, without isolation from the reaction mixture, or after isolation for the further reaction.
  • the compounds of the formulas XI, XII, XIII, XIV and XV are known compounds.
  • the compounds of the formula I are very effective in improving the light, heat and oxidation resistance of synthetic polymers such as, for example, high or low density polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / vinyl acetate copolymers, polybutadiene, polyisoprene, polystyrene, Butadiene / styrene copolymers, acrylonitrile / butadiene / styrene copolymers, polymers and copolymers of vinyl chloride and vinylidene chloride, polyoxymethylene, polyurethanes, saturated and unsaturated polyesters, polyamides, polycarbonates, polyacrylates, alkyd resins and epoxy resins.
  • synthetic polymers such as, for example, high or low density polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / vinyl acetate copolymers, polybutadiene, polyisoprene, polystyren
  • the compounds of the formula I can be used in a mixture with synthetic polymers in various proportions, which depend on the type of polymer, the end use and the presence of further additives. In general, it is expedient to use 0.01 to 5% by weight! the compound of formula I, based on the weight of the polymers, preferably 0.05 to 1%.
  • the compounds of the formula I can be incorporated into the polymeric materials by various methods, such as by dry mixing in powder form or wet mixing in the form of a solution or suspension or else in the form of a concentrated premix; the synthetic polymer can be used in the form of powder, granules, solution, suspension or latex.
  • the polymers stabilized with the products of the formula I can be used for the production of moldings, foils, binders, fibers, continuous filaments, lacquers, etc.
  • 2-Hydroxybenzophenones for example the 4-hydroxy, 4 - methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-Hydroxy-4,4'-dimethoxy derivative.
  • Esters of optionally substituted benzoic acids e.g. 4-tert.butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis- (4-tert.butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4-hydroxybenzoic acid-2,4-di-tert. butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.
  • Acrylates such as ⁇ -cyano-ß, ß-diphenylacrylic acid, ethyl or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-ß-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, a-carbomethoxy-p-methoxy-cinnamic acid- methyl ester, N- (ß-carbomethoxy-ß-cyanovinyl) -2-methyl-indoline.
  • Nickel compounds e.g. Nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands such as n- Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as methyl or ethyl esters, nickel complexes of ketoximes such as 2-hydroxy-4-methyl -phenyl-und- cylketonoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.
  • additional ligands such as n- Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldi
  • Sterically hindered amines e.g. Bis (2,2,6,6-tetramethylpiperidyl) sebacate bis (1,2,2,6,6-pentamethylpiperidyl) sebacate n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl- malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product from N, N '- (2nd , 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,
  • Oxalic acid diamides such as 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5 ' -di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl- oxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide, mixtures of ortho- and para-methoxy and of o- and p-ethoxy-di-substituted oxanilides.
  • Metal deactivators e.g. N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis-salicyloyl hydrazine, N, N'-bis (3, S-di-tert.butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.
  • N, N'-diphenyloxalic acid diamide e.g. N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis-salicyloyl hydrazine, N, N'-bis (3, S-di-tert.butyl-4-hydroxyphenylpropionyl) hydr
  • Phosphites and phosphonites e.g. Triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tri- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris- (2,4-di-tert.butylphenyl) phosphite, diisodhritol-diisodhritol-di -tert.butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert.butylphenyl) -4,4'-biphenylene diphosphonite.
  • Peroxide destroying compounds e.g. Esters of ß-thio-dipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakod (d) tetrakis ( ⁇ ).
  • Esters of ß-thio-dipropionic acid for example lauryl, stearyl, myristyl or tridecyl esters
  • mercaptobenzimidazole the zinc salt of 2-mercaptobenzimidazole
  • zinc dibutyl dithiocarbamate dioctadecyl disulfide
  • Polyamide stabilizers e.g. Copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.
  • Basic co-stabilizers such as e.g. Melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, Antimony catecholate or tin catecholate.
  • Basic co-stabilizers such as e.g. Melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate
  • Nucleating agents e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.
  • Fillers and reinforcing agents such as e.g. Calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.
  • additives such as Plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.
  • Example 1 35.1 g (0.1 mol) of 2- [N- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -4,6-dimethoxy-1,3,5-trizain , 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidin-4-ol, 0.3 g of sodium hydride and 200 ml of xylene are heated under reflux for 12 hours. The solvent is slowly distilled off together with the methanol formed during the reaction and replaced with the same volume of fresh solvent. The reaction mixture is evaporated to dryness and the residue is ground, washed with water and dried.
  • a product is obtained with mp. 205-215 ° C and average molecular weight Mn 4,300.
  • Example 4 26.8 g (0.1 mol) of 4-0ctylamino-2,2,6,6-tetramethylpiperidine slowly become a solution of 18.5 g (0.1 mol) of cyanuric chloride in 180 ml cooled to 0 ° C. Trimethylbenzene added, the temperature must not exceed 10 ° C. A solution of 4 g of sodium hydride in 50 ml of water is then added at the same temperature. 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidin-4-ol and 12 g of sodium hydroxide are added to the mixture thus obtained. The mixture is refluxed for 20 hours and the water is removed azeotropically.
  • Example 7 20.4 g (0.05 mol) of 2,4-dimethoxy-6- [N- (2,2,6,6-tetramethyl-piperdin-4-yl) octylamino] -1,3,5 triazine, 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidin-4-ol, 0.25 g of sodium and 200 ml of xylene are boiled under reflux for 8 hours . The solvent is slowly distilled off together with the methanol formed during the reaction and replaced with the same volume of fresh solvent.
  • the mixture is cooled to 80 ° C., then 7.3 g (0.05 mol) of dimethyl succinate are added and the mixture is refluxed for a further 8 hours, with continued replacement of the solvent.
  • the product obtained melts at 95-103 ° C and has an average molecular weight Mn of 3,700.
  • Example 8 Repeating the procedure described in Example 7 with 17.55 g (0.05 mol) of 2- [N- (2,2,6,6-tetramethyl-piperidin-4-yl) butylamino] -4, 6-dimethoxy-1,3,5-triazine, 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-piperidin-4-ol and 7.3 g (0.05 mol) of dimethyl succinate as starting products, a product is obtained with mp. 125-134 ° C. and average molecular weight Mn 2,000.
  • Example 9 2 g each of the compounds listed in Table 1 and 1 g of pentaerythritol tetrakis-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (antioxidant) are mixed with 1000 g of polypropylene with a melt index of 2.4 (®Propathen HF 18, product of Imperial Chemical Industries) and 1 g calcium stearate intimately mixed.
  • polypropylene with a melt index of 2.4 (®Propathen HF 18, product of Imperial Chemical Industries) and 1 g calcium stearate intimately mixed.
  • Example 10 2.5 g each of the compounds listed in Table 2 and 1 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (antioxidant) are mixed with 1000 g of polypropylene with a Melt index of 13 (®Propathen HF 85, product of Imperial Chemical Industries), 1 g calcium stearate and 2.5 g titanium dioxide (®KRONOS RN 57) intimately mixed.
  • the fibers obtained are placed on white cardboard in a Weather-Ometer.65 WR at a black board temperature of 63 ° C.
  • the T 50 value is determined as described in Example 9.

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Abstract

Polymere Triazin-piperidylether der Formel I <IMAGE> worin R3 und R5 unabhängig voneinander eine der Gruppen der Formeln III, IV, V oder VI <IMAGE> <IMAGE> bedeuten und R5 zusätzlich eine Gruppe der Formel VII <IMAGE> sein kann, und R4 C2-C18 Diacyl oder eine Gruppe der Formel VIII <IMAGE> ist, eignen sich besonders gut zum Stabilisieren von synthetischen Polymeren gegen die Einwirkung von Licht. Für die Bedeutung von a), b), R1, R2, R7, X und Y wird auf Anspruch 1 verwiesen.Polymeric triazine piperidyl ethers of the formula I <IMAGE> in which R3 and R5 independently of one another are one of the groups of the formulas III, IV, V or VI <IMAGE> <IMAGE> and R5 can additionally be a group of the formula VII <IMAGE>, and R4 C2-C18 is diacyl or a group of the formula VIII <IMAGE> are particularly suitable for stabilizing synthetic polymers against the action of light. For the meaning of a), b), R1, R2, R7, X and Y, reference is made to claim 1.

Description

Die vorliegende Erfindung betrifft neue Piperidylreste enthaltende polymere Verbindungen, welche als Stabilisatoren für synthetische Poylmeren gegen lichtinduzierten, thermischen oder oxidativen Abbau verwendet werden können.The present invention relates to new piperidyl radical-containing polymeric compounds which can be used as stabilizers for synthetic polymers against light-induced, thermal or oxidative degradation.

Hydroxygruppen enthaltende Polyether mit Polyalkylpiperidylaminogruppen sind in US Patent Nr. 4 294 963 als Stabilisatoren für Polymeren beschrieben. Neue polymere Triazin-piperidylester sind nun gefunden worden, die in synthetischen Polymeren eine ausserordentliche Lichtschutzwirkung zeigen.Hydroxy group-containing polyethers with polyalkylpiperidylamino groups are described in US Patent No. 4,294,963 as stabilizers for polymers. New polymeric triazine piperidyl esters have now been found which show an extraordinary light protection effect in synthetic polymers.

Demnach betrifft die vorliegende Erfindung Verbindungen der Formel I

Figure imgb0001
worin R1 und R2 unabhängig voneinander Wasserstoff, C1-C18 Alkyl, durch Hydroxy, C1-C18 Alkoxy oder C2-C18 Dialkylamino substituiertes C 2-C 12 Alkyl, C 3-C 18 Alkenyl, C5-C18 Cycloalkyl, C 6-C18 Aryl, C7-C18 Aralkyl oder eine Gruppe der Formel II
Figure imgb0002
bedeuten, worin R6 Wasserstoff, C1-C12 Alkyl, C3-C12 Alkenyl oder Alkynyl, C7-C12 Aralkyl oder C1-C12 Acyl ist, oder R1 und R2 zusammen mit dem Stickstoffatom an dem sie gebunden sind einen heterocyclischen Rest ausgewählt aus der Gruppe bestehend aus Pyrrolidin-1-yl, Piperidin-1-yl, Hexahydroazepin-1-yl, Morpholin-4-yl und 4-Methylpiperazin-l-yl bilden, R3 und R5 unabhängig voneinander eine der Gruppen der Formeln III, IV, V oder VI
Figure imgb0003
Figure imgb0004
bedeuten und R5 zusätzlich eine Gruppe der Formel VII
Figure imgb0005
sein kann, worin R7 Wasserstoff, C1-C6 Alkyl oder Phenyl ist, X eine Gruppe -O-(CH2)n-O- oder -N(R8)-C(O)-(CH2)n-C(O)-N(R8)- bedeutet, n eine Zahl von 1 bis 6 ist, R die gleiche Bedeutung wie R1 und R2 hat und Y C2-C12 Alkylen, durch eine Hydroxygruppe substituiertes oder durch ein Sauerstoffatom unterbrochenes C 3-C 12 Alkylen, C 4-C 12 Alkenylen oder C8-C12 Aralkylen bedeutet, R4 C2-C18 Diacyl oder eine Gruppe der Formel VIII
Figure imgb0006
 Accordingly, the present invention relates to compounds of the formula I.
Figure imgb0001
 wherein R 1 and R 2 are independently hydrogen, C 1 -C 18 alkyl, by hydroxy, C 1 -C 18 alkoxy or C 2 -C 18 dialkylamino-substituted C 2 - C 12 alkyl, C 3 - C 18 alkenyl, C 5 -C 18 cycloalkyl, C 6 -C 18 aryl, C 7 -C 18 aralkyl or a group of formula II
Figure imgb0002
 mean, wherein R 6 is hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkenyl or alkynyl, C 7 -C 12 aralkyl or C 1 -C 12 acyl, or R 1 and R 2 together with the nitrogen atom on the they are bonded to form a heterocyclic radical selected from the group consisting of pyrrolidin-1-yl, piperidin-1-yl, hexahydroazepin-1-yl, morpholin-4-yl and 4-methylpiperazin-l-yl, R 3 and R 5 independently of one another one of the groups of the formulas III, IV, V or VI
Figure imgb0003
Figure imgb0004
 mean and R 5 additionally represents a group of formula VII
Figure imgb0005
 where R 7 is hydrogen, C 1 -C 6 alkyl or phenyl, X is a group -O- (CH 2 ) n -O- or -N (R 8 ) -C (O) - (CH 2 ) n -C (O) -N (R 8 ) - means n is a number from 1 to 6, R has the same meaning as R 1 and R 2 and YC 2 -C 12 alkylene, substituted by a hydroxyl group or by an oxygen atom interrupted C 3 - C 12 alkylene, C 4 - C 12 alkenylene or C 8 -C 12 aralkylene, R 4 C 2 -C 18 diacyl or a group of the formula VIII
Figure imgb0006

ist, worin R1 und R2 die oben angegebene Bedeutung haben, a eine Zahl zwischen 0,2 und 1 und b eine Zahl zwischen Null und 0,8 sind, wobei die Verbindungen der Formel I ein mittleres Molekulargewicht Mn zwischen 1'000 und 20'000 aufweisen.in which R 1 and R 2 have the meaning given above, a is a number between 0.2 and 1 and b is a number between zero and 0.8, the compounds of the formula I having an average molecular weight Mn between 1,000 and Have 20,000.

Die Bedeutungen der verschiedenen Reste speziell erläuternde Beispiele sind wie folgt:

  • Für R1, R2 und R8: Wasserstoff, Methyl, Ethyl, Propyl, Isopropyl, Butyl, But-2-yl, Isobutyl, Hexyl, 2-Ethylhexyl, Octyl, Decyl, Dodecyl, Hexadecyl, Octadecyl, 2-Hydroxyethyl, 3-Hydroxypropyl, 2-Methoxyethyl, 2-Ethoxyethyl, 3-Methoxpropyl, 3-Ethoxypropyl, 3-Octyloxypropyl, 3-Dodecyloxypropyl, 3-Octadecyloxypropyl, 3-Dimethylaminopropyl, 3-Diethylaminopropyl, 4-Diethylaminobutyl, Allyl, Methallyl, But-2-enyl, Undec-10-enyl, Oleyl, Cyclohexyl, Methylcyclohexyl, Trimethylcyclohexyl, Cyclooctyl, Cyclododecyl, Phenyl, Methylphenyl, Dimethylphenyl, Trimethylphenyl, t-Butylphenyl, t-Octylphenyl, Methoxyphenyl, Ethoxyphenyl, 3,5-Di-t-butyl-4-hydroxyphenyl, Benzyl, Methylbenzyl, Hydroxybenzyl, 3,5-Di-t-butyl-4-hydroxybenzyl, 2,2,6,6-Tetramethyl-piperidin-4-yl, 1,2,2,6,6-Pentamethyl-piperidin-4-yl, 1-Allyl-2,2,6,6-tetramethyl-piperidin-4-yl, 1=Berizyl-2,-2,6,6-tetramethyl-piperidin-4-yl and 1-Acetyl-2,2,6,6-tetramethyl-piperidin-4-yl;
  • Für R4: Oxalyl, Malonyl, Succinyl, Glutaryl, Adipoyl, Sebacoyl, Isophthaloyl, Terephthaloyl oder eine Gruppe der Formel (V), worin R1 und R2 die oben angegebene Bedeutung haben;
  • Für R6: Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Hexyl, Octyl, Decyl, Dodecyl, Allyl, Methallyl, But-2-enyl, Hex-2-enyl, Propargyl, Benzyl, Methylbenzyl, t-Butylbenzyl, Hydroxybenzyl, Acetyl, Propionyl, Butyryl, Caproyl und Benzoyl;
  • Für R7: Wasserstoff, Methyl, Ethyl, Propyl, Butyl, Hexyl und Phenyl, Für Y: Ethylen, Trimethylen, Tetramethylen, Hexamethylen, Octamethylen, Decamethylen, Dodecamethylen, 2-Hydroxypropan-1,3-diyl, 3-Oxapentan-1,5-diyl, But-2-en-l,4-diyl und Xylylen.
The meanings of the various residues, specifically illustrative examples, are as follows:
  • For R 1 , R 2 and R 8 : hydrogen, methyl, ethyl, propyl, isopropyl, butyl, but-2-yl, isobutyl, hexyl, 2-ethylhexyl, octyl, decyl, dodecyl, hexadecyl, octadecyl, 2-hydroxyethyl, 3-hydroxypropyl, 2-methoxyethyl, 2-ethoxyethyl, 3-methoxypropyl, 3-ethoxypropyl, 3-octyloxypropyl, 3-dodecyloxypropyl, 3-octadecyloxypropyl, 3-dimethylaminopropyl, 3-diethylaminopropyl, 4-diethylaminobutyl, allyl, methallyl, but- 2-enyl, undec-10-enyl, oleyl, cyclohexyl, methylcyclohexyl, trimethylcyclohexyl, cyclooctyl, cyclododecyl, phenyl, methylphenyl, dimethylphenyl, trimethylphenyl, t-butylphenyl, t-octylphenyl, methoxyphenyl, ethoxyphenyl, 3,5-di-t- butyl-4-hydroxyphenyl, benzyl, methylbenzyl, hydroxybenzyl, 3,5-di-t-butyl-4-hydroxybenzyl, 2,2,6,6-tetramethyl-piperidin-4-yl, 1,2,2,6, 6-pentamethyl-piperidin-4-yl, 1-allyl-2,2,6,6-tetramethyl-piperidin-4-yl, 1 = berizyl-2, -2,6,6-tetramethyl-piperidin-4-yl and 1-acetyl-2,2,6,6-tetramethyl-piperidin-4-yl;
  • For R 4 : oxalyl, malonyl, succinyl, glutaryl, adipoyl, sebacoyl, isophthaloyl, terephthaloyl or a group of the formula (V), in which R 1 and R2 have the meaning given above;
  • For R 6 : hydrogen, methyl, ethyl, propyl, butyl, hexyl, octyl, decyl, dodecyl, allyl, methallyl, but-2-enyl, hex-2-enyl, propargyl, benzyl, methylbenzyl, t-butylbenzyl, hydroxybenzyl, Acetyl, propionyl, butyryl, caproyl and benzoyl;
  • For R 7 : hydrogen, methyl, ethyl, propyl, butyl, hexyl and phenyl, for Y: ethylene, trimethylene, tetramethylene, hexamethylene, octamethylene, decamethylene, dodecamethylene, 2-hydroxypropane-1,3-diyl, 3-oxapentane-1 , 5-diyl, but-2-en-l, 4-diyl and xylylene.

Von besonderem Interesse sind die Verbindungen der Formel I, worin R1 und R2 unabhängig voneinander Wasserstoff, C1-C12 Alkyl, durch C1-C12 Alkoxy substituiertes C2-C6 Alkyl, C 3-C 6 Alkenyl, C6-C10 Cycloalkyl oder eine Gruppe der Formel II bedeuten, worin R6 Wasserstoff, Methyl, Allyl, Benzyl oder Acetyl ist, oder R1 und R2 zusammen mit dem Stickstoffatom an dem sie gebunden sind Pyrrolidin-l-yl, Piperidin-1-yl, Hexahydroazepin-1-yl oder Morpholin-4-yl bilden, R3 und R5 eine Gruppe der Formel III sind und R5 zusätzlich eine Gruppe der Formel VII sein kann, R7 Wasserstoff, Methyl oder Ethyl ist, Y C2-C6 Alkylen, But-2-en-1,4-diyl oder Xylylen bedeutet, R4 C2-C12 Diacyl oder eine Gruppe der Formel VIII ist, worin R1 und R2 die oben angegebene Bedeutung haben, a eine Zahl zwischen 0,3 und 1 und b eine Zahl zwischen Null und 0,7 bedeuten, wobei die Verbindungen der Formel I ein mittleres Molekulargewicht Mn zwischen 1'500 und 10'000 aufweisen.Of particular interest are the compounds of the formula I in which R 1 and R 2 independently of one another are hydrogen, C 1 -C 12 alkyl, C 2 -C 6 alkyl substituted by C 1 -C 12 alkoxy, C 3 - C 6 alkenyl, C 6 -C 10 cycloalkyl or a group of the formula II in which R 6 is hydrogen, methyl, allyl, benzyl or acetyl, or R 1 and R 2 together with the nitrogen atom to which they are attached pyrrolidin-l-yl, piperidine Form 1-yl, hexahydroazepin-1-yl or morpholin-4-yl, R 3 and R 5 are a group of the formula III and R 5 can additionally be a group of the formula VII, R 7 is hydrogen, methyl or ethyl, YC 2 -C 6 alkylene, but-2-ene-1,4-diyl or xylylene, R 4 is C 2 -C 12 diac y l or a group of the formula VIII, in which R 1 and R 2 have the meaning given above , a is a number between 0.3 and 1 and b is a number between zero and 0.7, the compounds of the formula I having an average molecular weight Mn between 1,500 and 10,000.

Bevorzugt sind Verbindungen der Formel I, worin R1 und R2 unabhängig voneinander C1-C8 Alkyl, Cyclohexyl, 2,2,6,6-Tetramethylpiperidin-4-yl oder 1,2,2,6,6-Pentamethylpiperidin-4-yl bedeuten, R3 und R5 eine Gruppe der Formel III sind und R5 zusätzlich eine Gruppe der Formel VII sein kann, R7 Wasserstoff oder Methyl ist, Y But-2-en-1,4-diyl oder Xylylen bedeutet, a die Zahl 1 und b Null bedeuten, wobei die Verbindungen der Formel I ein mittleres Molekulargewicht Mn zwischen 1'500 und 6'000 aufweisen.Preferred compounds of the formula I are those in which R 1 and R 2 independently of one another are C 1 -C 8 alkyl, cyclohexyl, 2,2,6,6-tetramethylpiperidin-4-yl or 1,2,2,6,6-pentamethylpiperidine 4-yl, R 3 and R 5 are a group of the formula III and R 5 can additionally be a group of the formula VII, R 7 is hydrogen or methyl, Y is but-2-ene-1,4-diyl or xylylene , a is the number 1 and b is zero, the compounds of the formula I having an average molecular weight Mn between 1,500 and 6,000.

Verbindungen der Formel I, worin b nicht Null bedeutet, können hergestellt werden durch Umsetzung einer Mischung von Verbindungen der Formeln IX und X

Figure imgb0007
worin R1, R2 und R4 die oben angegebene Bedeutung haben und A1, A2, A3 und A4 Cl oder C1-C4 Alkxoy bedeuten, mit einer der Verbindungen der folgenden Formeln XI, XII, XIII oder XIV
Figure imgb0008
Figure imgb0009
und, wenn R5 eine Gruppe der Formel VII ist, zusätzlich mit einer Verbindung der Formel XV
Figure imgb0010
worin R7, X und Y die oben angebeene Bedeutung haben, vorzugsweise im stöchiomietrischen Verhältnis.Compounds of the formula I in which b is not zero can be prepared by reacting a mixture of compounds of the formulas IX and X
Figure imgb0007
 wherein R 1 , R 2 and R 4 have the meaning given above and A 1 , A 2 , A 3 and A 4 Cl or C 1 -C 4 Alkxoy, with one of the compounds of the following formulas XI, XII, XIII or XIV
Figure imgb0008
Figure imgb0009
 and, if R 5 is a group of the formula VII, additionally with a compound of the formula XV
Figure imgb0010
 wherein R 7 , X and Y have the meaning given above, preferably in a stoichiometric ratio.

Wenn b Null ist, werden die Verbindungen der Formel I durch Umsetzung einer Verbindung der Formel IX mit einer der Verbindungen der Formeln XI, XII, XIII oder XIV und gegebenenfalls XV in annähernd stöchiometrischem Verhältnis hergestellt.If b is zero, the compounds of the formula I are prepared by reacting a compound of the formula IX with one of the compounds of the formulas XI, XII, XIII or XIV and optionally XV in an approximately stoichiometric ratio.

In beiden Fällen kann die Reaktion ohne oder mit einem inerten organischen Lösungsmittel durchgeführt werden, in Gegenwart einer organischen oder anorganischen Base, wenn A1, A2, A3 und A4 Cl bedeuten, oder eines Umesterungskatalysators, wenn A1, A2, A3 und A4 Alkoxy sind.In both cases, the reaction can be carried out without or with an inert organic solvent, in the presence of an organic or inorganic base if A 1 , A 2 , A 3 and A 4 are Cl, or a transesterification catalyst if A 1 , A 2 , A 3 and A 4 are alkoxy.

Als Lösungsmittel eignen sich z.B. Benzol, Toluol, Xylol, Ethylbenzol, Trimethylbenzol, Tetralin, Decalin, Octan, Decan, Gemische von alipahtischen Kohlenwasserstoffen mit Siedepunkt zwischen 100 und 200°C, Dioxan, Dibutylether, 1,2-Dimethoxyethan, 1,2-Diethoxyethan, Diethylenglykol-dimethylether und Diethylenglykoldiethylether, N,N-Dimethylformamid, N,N-Dimethalacetamid, N-Methylpyrrolidon und Dimethylsulfoxid.Suitable solvents are e.g. Benzene, toluene, xylene, ethylbenzene, trimethylbenzene, tetralin, decalin, octane, decane, mixtures of aliphatic hydrocarbons with a boiling point between 100 and 200 ° C, dioxane, dibutyl ether, 1,2-dimethoxyethane, 1,2-diethoxyethane, diethylene glycol dimethyl ether and diethylene glycol diethyl ether, N, N-dimethylformamide, N, N-dimethalacetamide, N-methylpyrrolidone and dimethyl sulfoxide.

Geeignete Basen, die (bei A1, A2, A3 und A4 = C1) zum Abfangen der sich bei der Reaktion bildenden Halogenwssertoffsäure eingesetzt werden, sind z.B. Pyridin, Triethylamin, Tributylamin, Natriumhydroxid, Kaliumhydroxid, Natriumcarbonat, Kaliumcarbonat. In jedem Fall wird die Base in mindestens der äquivalenten Menge der durch die Reaktion frei werdenden Halogenwasserstoffsäure eingesetzt.Suitable bases which are used (in the case of A 1 , A 2 , A 3 and A 4 = C1) to scavenge the hydrofluoric acid formed in the reaction are, for example, pyridine, triethylamine, tributylamine, sodium hydroxide, potassium hydroxide, sodium carbonate, potassium carbonate. In any case, the base is used in at least the equivalent amount of the hydrohalic acid released by the reaction.

Für die Fälle in denen A1, A2, A3 und A4 Alkoxy bedeuten, können als Umesterungskatalysatoren z.B. Alkalimetalle sowie deren Alkoholate, Hydride und Amide eingesetzt werden.For the cases in which A 1 , A 2 , A3 and A4 are alkoxy, it is possible, for example, to use alkali metals and their alcoholates, hydrides and amides as transesterification catalysts.

Die Polykondensation kann bei Temperaturen zwischen 80 und 280°C, bevorzugt zwischen 100 und 200°C im molaren Verhältnis Verbindung der Formel IX + Verbindung der Formel X: Verbindung der Formel XI, XII, XIII oder XIV + Verbindung der Formel XV zwischen 1,3:1 und 1:1,3, bevorzugt zwischen 1,2:1 und 1:1,2.The polycondensation can at temperatures between 80 and 280 ° C, preferably between 100 and 200 ° C in a molar ratio compound of formula IX + compound of formula X: compound of formula XI, XII, XIII or XIV + compound of formula XV between 1, 3: 1 and 1: 1.3, preferably between 1.2: 1 and 1: 1.2.

Die verschiedenen Edukte können gleichzeitig oder nacheinander umgesetzt werden.The different starting materials can be implemented simultaneously or in succession.

Die Verbindungen der Formel IX können in Analogie zu bekannten Verfahren, ausgehend von Cyanurchlorid, erhalten werden. Die erhaltenen Dichlortriazine oder Dialkoxytriazine können direkt, ohne Isolierung von der Reaktionsmischung, oder nach Isolierung zur weiteren Reaktion eingesetzt werden. Die Verbindungen der Formeln XI, XII, XIII, XIV und XV sind bekannte Verbindungen.The compounds of formula IX can be obtained analogously to known processes, starting from cyanuric chloride. The dichlorotriazines or dialkoxytriazines obtained can be used directly, without isolation from the reaction mixture, or after isolation for the further reaction. The compounds of the formulas XI, XII, XIII, XIV and XV are known compounds.

Wie anfangs erwähnt, sind die Verbindungen der Formel I sehr wirksam bei der Verbesserung der Licht-, Wärme- und Oxydationsbeständigkeit von synthetischen Polymeren wie beispielsweise Polyethylen hoher oder niedriger dichte, Polypropylen, Ethylen/ Propylencopoylmeren, Ethylen/Vinylacetatcopolymeren, Polybutadien, Polyisopren, Polystyrol, Butadien/Styrolcopolymeren, Acrylnitril/ Butadien/Styrolcopolymeren, Polymeren und Copolymeren von Vinylchlorid und Vinylidenchlorid, Polyoxymethylen, Polyurethanen, gesättigten und ungesättigten Polyestern, Polyamiden, Polycarbonaten, Polyacrylaten, Alkydharzen und Epoxidharzen.As mentioned at the beginning, the compounds of the formula I are very effective in improving the light, heat and oxidation resistance of synthetic polymers such as, for example, high or low density polyethylene, polypropylene, ethylene / propylene copolymers, ethylene / vinyl acetate copolymers, polybutadiene, polyisoprene, polystyrene, Butadiene / styrene copolymers, acrylonitrile / butadiene / styrene copolymers, polymers and copolymers of vinyl chloride and vinylidene chloride, polyoxymethylene, polyurethanes, saturated and unsaturated polyesters, polyamides, polycarbonates, polyacrylates, alkyd resins and epoxy resins.

Die Verbindungen der Formel I können im Gemisch mit synthetischen Polymeren in verschiedenen Anteilen eingesetzt werden, die von der Art des Polymeren, dem Endzweck und der Gegenwart weiterer Zusatzstoffe abhängen. Im allgemeinen setzt man zweckmässig 0,01 bis 5 Gew.-! der Verbindung der Formel I, bezogen auf das Gewicht der Polymeren, vorzugsweise 0,05 bis 1%, ein.The compounds of the formula I can be used in a mixture with synthetic polymers in various proportions, which depend on the type of polymer, the end use and the presence of further additives. In general, it is expedient to use 0.01 to 5% by weight! the compound of formula I, based on the weight of the polymers, preferably 0.05 to 1%.

Die Verbindungen der Formel I können nach verschiedenen Verfahren in die polymeren Materialien eingearbeitet werden, wie durch trockenes Einmischen in Pulverform oder nasses Einmischen in Form einer Lösung oder Suspension oder auch in Form eines konzentrierten Vorgemisches; das synthetische Polymer lässt sich dabei in Form von Pulver, Granulat, Lösung, Suspension oder Latex einsetzen. Die mit den Produkten der Formel I stabilisierten Polymeren lassen sich zur Herstellung von Formkörpern, Folien, Bindern, Fasern, Endlosfäden, Lacken usw. verwenden.The compounds of the formula I can be incorporated into the polymeric materials by various methods, such as by dry mixing in powder form or wet mixing in the form of a solution or suspension or else in the form of a concentrated premix; the synthetic polymer can be used in the form of powder, granules, solution, suspension or latex. The polymers stabilized with the products of the formula I can be used for the production of moldings, foils, binders, fibers, continuous filaments, lacquers, etc.

Gegebenenfalls kann man den Mischungen von Verbindungen der Formel I mit den synthetischen Polymeren weitere Zusatzstoffe beigegeben, wie beispielsweie Antioxydantien, UV-absorbierende Stoffe, Nickelstabilisatoren, Pigmente, Füllstoffe, Weichmacher, Antistatika, Flammschutzmittel, Schmierstoffe, Korrosionshemmstoffe sowie Metalldesaktivatoren. Beispiele für in Mischung mit Verbindungen der Formel I verwendbare Zsuatzstoffe sind insbesondere:If appropriate, further additives can be added to the mixtures of compounds of the formula I with the synthetic polymers, such as, for example, antioxidants, UV-absorbing substances, nickel stabilizers, pigments, fillers, plasticizers, antistatic agents, flame retardants, lubricants, corrosion inhibitors and metal deactivators. Examples of additives which can be used in a mixture with compounds of the formula I are in particular:

1. Antioxidantien1. Antioxidants 1.1. Alkylierte Monophenole1.1. Alkylated monophenols

  • 2,6-Di-tert.butyl-4-methylphenol2,6-di-tert-butyl-4-methylphenol
  • 2-Tert.butyl-4,6-dimethylphenol2-tert-butyl-4,6-dimethylphenol
  • 2,6-Di-tert.butyl-4-ethylphenol2,6-di-tert-butyl-4-ethylphenol
  • 2,6-Di-tert.butyl-4-n-butylphenol2,6-di-tert-butyl-4-n-butylphenol
  • 2,6-Di-tert.butyl-4-i-butylphenol2,6-di-tert-butyl-4-i-butylphenol
  • 2,6-Di-cyclopentyl-4-methylphenol2,6-di-cyclopentyl-4-methylphenol
  • 2-(a-Methylcyclohexyl)-4,6-dimethylphenol2- (a-methylcyclohexyl) -4,6-dimethylphenol
  • 2,6-Di-octadecyl-4-methylphenol2,6-di-octadecyl-4-methylphenol
  • 2,4,6-Tri-cyclohexylphenol2,4,6-tri-cyclohexylphenol
  • 2,6-Di-tert.butyl-4-methoxymethylphenol2,6-di-tert-butyl-4-methoxymethylphenol
1.2. Alkylierte Hydrochinone1.2. Alkylated hydroquinones

  • 2,6-Di-tert.butyl-4-methoxyphenol2,6-di-tert-butyl-4-methoxyphenol
  • 2,5-Di-tert.butyl-hydrochinon2,5-di-tert-butyl hydroquinone
  • 2,5-Di-tert.amyl-hydrochinon2,5-di-tert-amyl hydroquinone
  • 2,6-Diphenyl-4-octadecyloxyphenol2,6-diphenyl-4-octadecyloxyphenol
1.3. Hydroxylierte Thiodiphenylether1.3. Hydroxylated thiodiphenyl ether

  • 2,2'-Thio-bis-(6-tert.butyl-4-methylphenol)2,2'-thio-bis- (6-tert-butyl-4-methylphenol)
  • 2,2'-Thio-bis-(4-octylphenol)2,2'-thio-bis- (4-octylphenol)
  • 4,4'-Thio-bis-(6-tert.butyl-3-methylphenol)4,4'-thio-bis- (6-tert.butyl-3-methylphenol)
  • 4,4'-Thio-bis-(6-tert.butyl-2-methylphenol)4,4'-thio-bis- (6-tert-butyl-2-methylphenol)
1.4. Alkyliden-Bisphenole1.4. Alkylidene bisphenols

  • 2,2'-Methylen-bis-(6-tert.butyl-4-methylphenol)2,2'-methylene-bis- (6-tert-butyl-4-methylphenol)
  • 2,2'-Methylen-bis-(6-tert.butyl-4-ethylphenol)2,2'-methylene-bis- (6-tert.butyl-4-ethylphenol)
  • 2,2'-Methylen-bis-[4-methyl-6-(a-methylcyclohexyl)-phenoll2,2'-methylene-bis- [4-methyl-6- (a-methylcyclohexyl) phenol
  • 2,2'-Methylen-bis-(4-methyl-6-cyclohexylphenol)2,2'-methylene-bis- (4-methyl-6-cyclohexylphenol)
  • 2,2'-Methylen-b is-(6-nonyl-4-methylphenol)2,2'-methylene-b is- (6-nonyl-4-methylphenol)
  • 2,2'-Methylen-bis-(4,6-di-tert.butylphenol)2,2'-methylene-bis- (4,6-di-tert-butylphenol)
  • 2,2'-Ethyliden-bis-(4,6-di-tert.butylphenol)2,2'-ethylidene-bis- (4,6-di-tert-butylphenol)
  • 2,2'-Ethyliden-bis-(6-tert.butyl-4-isobutylphenol)2,2'-ethylidene-bis- (6-tert-butyl-4-isobutylphenol)
  • 2,2'-Methylen-bis-[6-(a-methylbenzyl)-4-nonylphenol]2,2'-methylene-bis- [6- (a-methylbenzyl) -4-nonylphenol]
  • 2,2'-Methlyen-bis-[6-(α,α-dimethylbenzyl)-4-nonylphenol]2,2'-methylene-bis- [6- (α, α-dimethylbenzyl) -4-nonylphenol]
  • 4,4'-Methylen-bis-(2,6-di-tert.butylphenol)4,4'-methylene-bis- (2,6-di-tert-butylphenol)
  • 4,4'-Methylen-bis-(6-tert.butyl-2-methylphenol)4,4'-methylene-bis- (6-tert-butyl-2-methylphenol)
  • 1,1-Bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butan1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) butane
  • 2,6-Di-(3-tert.butyl-5-methyl-2-hydroxybenzyl)-4-methylphenol2,6-di- (3-tert-butyl-5-methyl-2-hydroxybenzyl) -4-methylphenol
  • 1,1,3-Tris-(5-tert.butyl-4-hydroxy-2-methylphenyl)-butan1,1,3-tris (5-tert-butyl-4-hydroxy-2-methylphenyl) butane
  • 1,1-Bis-(5-tert.butyl-4-hydroxy-2-methylphenyl)-3-n-dodecylmercapto- butan1,1-bis (5-tert-butyl-4-hydroxy-2-methylphenyl) -3-n-dodecylmercapto-butane

Ethylenglycol-bis-[3,3-bis-(3'-tert.butyl-4'-hydroxyphenyl)-butyrat] Di-(3-tert .butyl-4-hydroxy-5-methylphenyl)-dicyclopentadien Di-[2-(3'-tert.butyl-2'-hydroxy-5'-methyl-benzyl)-6-tert.butyl-4-methyl-phenyl]-terephthalat.Ethylene glycol bis [3,3-bis (3'-tert-butyl-4'-hydroxyphenyl) butyrate] di- (3-tert-butyl-4-hydroxy-5-methylphenyl) dicyclopentadiene di- [2 - (3'-tert-butyl-2'-hydroxy - 5'-methyl-benzyl) -6-tert-butyl-4-methyl-phenyl] terephthalate.

1.5 Benzylverbindungen1.5 benzyl compounds

1,3,5-Tri-(3,5-di-tert.butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzol Di-(3,5-di-tert.butyl-4-hydroxybenzyl)-sulfid 3,5-di-tert.butyl-4-hydroxybenzyl-mercaptoessigsäure-isooctylester Bis-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)dithiol-terephthalat 1,3,5-Tris-(3,5-di-tert.butyl-4-hydroxybenzyl)-isocyanurat 1,3,5-Tris-(4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl)-isocyanurat 3,5-Di-tert.butyl-4-hydroxybenzyl-phosphonsäure-dioctadecylester 3,5-Di-tert.butyl-4-hydroxybenzyl-phosphonsäure-monoethylester, Calcium-salz.1,3,5-tri (3,5-di-tert-butyl-4-hydroxybenzyl) -2,4,6-trimethylbenzene di- (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide 3,5-di-tert.butyl-4-hydroxybenzyl-mercaptoacetic acid isooctyl ester bis- (4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl) dithiol terephthalate 1,3,5-tris- (3, 5-di-tert-butyl-4-hydroxybenzyl) isocyanurate 1,3,5-tris (4-tert.butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate 3,5-di-tert.butyl -4-hydroxybenzylphosphonic acid dioctadecyl ester 3,5-di-tert.butyl-4-hydroxybenzylphosphonic acid monoethyl ester, calcium salt.

1.6. Acylaminophenole1.6. Acylaminophenols

  • 4-Hydroxy-laurinsäureanilid4-hydroxy lauric anilide
  • 4-Hydroxy-stearinsäureanilid4-hydroxy stearic anilide
  • 2,4-Bis-octylmercapto-6-(3,5-di-tert.butyl-4-hydroxyanilino)-s-triazin2,4-bis-octylmercapto-6- (3,5-di-tert-butyl-4-hydroxyanilino) -s-triazine
  • N-(3,5-di-tert.butyl-4-hydroxyphenyl)-carbaminsäureoctylester.N- (3,5-di-tert-butyl-4-hydroxyphenyl) carbamic acid octyl ester.
1.7. Ester der ß-(3,5-Di-tert.butyl-4-hydroxyphenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen, wie z.B. mit1.7. Esters of .beta. (3,5-di-t-Bu t yl-4-hydroxyphenyl) propionic acid with mono- or polyhydric alcohols, for example with

  • Methanol DiethylenglycolMethanol diethylene glycol
  • Octadecanol TriethylenglycolOctadecanol triethylene glycol
  • 1,6-Hexandiol Pentaerythrit1,6-hexanediol pentaerythritol
  • Neopentylglycol Tris-hydroxyethyl-isocyanuratNeopentyl glycol tris-hydroxyethyl isocyanurate
  • Thiodiethylenglycol Di-hydroxyethyl-oxalsäurediamidThiodiethylene glycol di-hydroxyethyl oxalic acid diamide
1.8. Ester der β-(5-tert.butyl-4-hydroxy-3-methylphenyl)-propionsäure mit ein- oder mehrwertigen Alkoholen, wie z.B. mit1.8. Esters of β- (5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with mono- or polyhydric alcohols, e.g. With

  • Methanol DiethylenglycolMethanol diethylene glycol
  • Octadecanol TriethylenglycolOctadecanol triethylene glycol
  • 1,6-Hexandiol Pentaerythrit1,6-hexanediol pentaerythritol
  • Neopentylglycol Tris-hydroxyethyl-isocyanuratNeopentyl glycol tris-hydroxyethyl isocyanurate
  • Thiodiethylenglycol Di-hydroxyethyl-oxalsäurediamidThiodiethylene glycol di-hydroxyethyl oxalic acid diamide
1.9. Amide der β-(3,5-Di-tert.butyl-4-hydroxyphenyl)-propionsäure, wie z.B.1.9. Amides of β- (3,5-di-tert-butyl-4-hydroxyphenyl) propionic acid, e.g.

N,N'-Di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-hexamethylendiaminN, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hexamethylene diamine

N,N'-Di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-trimethylen- diaminN, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) trimethylene diamine

N,N'-Di-(3,5-di-tert.butyl-4-hydroxyphenylpropionyl)-hydrazinN, N'-di- (3,5-di-tert-butyl-4-hydroxyphenylpropionyl) hydrazine

2. UV-Absorber und Lichtschutzmittel2. UV absorbers and light stabilizers

2.1. 2-(2'-Hydroxyphenyl)-benztriazole, wie z.B. das 5'-Methyl-, 3',5'-Di-tert.butyl-, 5'-Tert.butyl-, 5'-(1,1,3,3-Tetramethylbutyl)-, 5-Chlor-3',5'-di-tert.butyl-, 5-Chlor-3'-tert.butyl-5'-methyl-, 3'-sec.Butyl-5'-tert.butyl, 4'-0ctoxy-, 3',5'-Di- tert.amyl-, 3',5'-Bis-(a,a-dimethylbenzyl)-Derivat.2.1. 2- (2'-hydroxyphenyl) benzotriazoles, e.g. the 5'-methyl, 3 ', 5'-di-tert-butyl, 5'-tert-butyl, 5' - (1,1,3,3-tetramethylbutyl) -, 5-chloro-3 ' , 5'-di-tert-butyl-, 5-chloro-3'-tert-butyl-5'-methyl-, 3'-sec-butyl-5'-tert-butyl, 4'-octoxy-, 3 ' , 5'-Di- tert.amyl-, 3 ', 5'-bis (a, a-dimethylbenzyl) derivative.

2.2. 2-Hydroxybenzophenone, wie z.B. das 4-Hydroxy-, 4-Methoxy-, 4-Octoxy-, 4-Decyloxy-, 4-Dodecyloxy-, 4-Benzyloxy-, 4,2',4'-Trihydroxy-, 2'-Hydroxy-4,4'-dimethoxy-Derivat.2.2. 2-Hydroxybenzophenones, for example the 4-hydroxy, 4 - methoxy, 4-octoxy, 4-decyloxy, 4-dodecyloxy, 4-benzyloxy, 4,2 ', 4'-trihydroxy, 2'-Hydroxy-4,4'-dimethoxy derivative.

2.3. Ester von gegebenenfalls substituierten Benzoesäuren, wie z.B. 4-Tert.butyl-phenylsalicylat, Phenylsalicylat, Octylphenylsalicylat, Dibenzoylresorcin, Bis-(4-tert.butylbenzoyl)-resorcin, Benzoylresorcin, 3,5-Di-tert.butyl-4-hydroxybenzoesäure-2,4-di- tert.butylphenylester, 3,5-Di-tert.butyl-4-hydroxybenzoesäurehexa- decylester.2.3. Esters of optionally substituted benzoic acids, e.g. 4-tert.butylphenylsalicylate, phenylsalicylate, octylphenylsalicylate, dibenzoylresorcinol, bis- (4-tert.butylbenzoyl) -resorcinol, benzoylresorcinol, 3,5-di-tert.butyl-4-hydroxybenzoic acid-2,4-di-tert. butylphenyl ester, 3,5-di-tert-butyl-4-hydroxybenzoic acid hexadecyl ester.

2.4. Acrylate, wie z.B. a-Cyan-ß,ß-diphenylacrylsäure-ethylester bzw. -isooctylester, a-Carbomethoxy-zimtsäuremethylester, a-Cyano-ß-methyl-p-methoxy-zimtsäuremethylester bzw. -butylester, a-Carbomethoxy-p-methoxy-zimtsäure-methylester, N-(ß-Carbomethoxy-ß-cyanovinyl)-2-methyl-indolin.2.4. Acrylates such as α-cyano-ß, ß-diphenylacrylic acid, ethyl or isooctyl ester, a-carbomethoxy-cinnamic acid methyl ester, a-cyano-ß-methyl-p-methoxy-cinnamic acid methyl ester or -butyl ester, a-carbomethoxy-p-methoxy-cinnamic acid- methyl ester, N- (ß-carbomethoxy-ß-cyanovinyl) -2-methyl-indoline.

2.5. Nickelverbindungen, wie z.B. Nickelkomplexe des 2,2'-Thio-bis-[4-(1,l,3,3-tetramethylbutyl)-phenols], wie der 1:1- oder der 1:2-Komplex, gegebenenfalls mit zusätzlichen Liganden wie n-Butylamin, Triethanolamin oder N-Cyclohexyl-diethanolamin, Nickeldibutyldithiocarbamat, Nickelsalze von 4-Hydroxy-3,5-di-tert.butylbenzyl- phosphonsäure-monoalkylestern wie vom Methyl- oder Ethylester, Nickelkomplexe von Ketoximen wie von 2-Hydroxy-4-methyl-phenyl-unde- cylketonoxim, Nickelkomplexe des 1-Phenyl-4-lauroyl-5-hydroxy-pyra- zols, gegebenenfalls mit zusätzlichen Liganden.2.5. Nickel compounds, e.g. Nickel complexes of 2,2'-thio-bis- [4- (1,1,3,3-tetramethylbutyl) phenol], such as the 1: 1 or the 1: 2 complex, optionally with additional ligands such as n- Butylamine, triethanolamine or N-cyclohexyl-diethanolamine, nickel dibutyldithiocarbamate, nickel salts of 4-hydroxy-3,5-di-tert-butylbenzylphosphonic acid monoalkyl esters such as methyl or ethyl esters, nickel complexes of ketoximes such as 2-hydroxy-4-methyl -phenyl-und- cylketonoxime, nickel complexes of 1-phenyl-4-lauroyl-5-hydroxy-pyrazole, optionally with additional ligands.

2.6. Sterisch gehinderte Amine, wie z.B. Bis-(2,2,6,6-tetramethylpiperidyl)-sebacat Bis-(1,2,2,6,6-pentamethylpiperidyl)-sebacat n-Butyl-3,5-di-tert.butyl-4-hydroxybenzyl-malonsäure-bis(1,2,2,6,6-pentamethylpiperidyl)-ester, Kondensationsprodukt aus 1-Hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidin und Bernsteinsäure, Kondensationsprodukt aus N,N'-(2,2,6,6-Tetramethyl-4-piperidyl)-hexamethylendiamin und 4-tert.Octylamino-2,6-dichlor-1,3,5-s-triazin,2.6. Sterically hindered amines, e.g. Bis (2,2,6,6-tetramethylpiperidyl) sebacate bis (1,2,2,6,6-pentamethylpiperidyl) sebacate n-butyl-3,5-di-tert-butyl-4-hydroxybenzyl- malonic acid bis (1,2,2,6,6-pentamethylpiperidyl) ester, condensation product from 1-hydroxyethyl-2,2,6,6-tetramethyl-4-hydroxypiperidine and succinic acid, condensation product from N, N '- (2nd , 2,6,6-tetramethyl-4-piperidyl) hexamethylenediamine and 4-tert-octylamino-2,6-dichloro-1,3,5-s-triazine,

Tris-(2,2,6,6-tetramethyl-4-piperidyl)-nitrilotriacetat, Tetrakis-(2,2,6,6-tetramethyl-4-piperidyl)-1,2,3,4-butantetracarbon- säure,Tris (2,2,6,6-tetramethyl-4-piperidyl) nitrilotriacetate, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarbonic acid,

1,1'-(1,2-Ethandiyl)-bis-(3,3,5,5-tetramethyl-piperazinon).1,1 '- (1,2-ethanediyl) bis (3,3,5,5-tetramethyl-piperazinone).

2.7. Oxalsäurediamide, wie z.B. 4,4'-Di-octyloxy-oxanilid, 2,2'-Di-octyloxy-5,5'-di-tert.butyl-oxanilid, 2,2'-Di-dodecyloxy-5,5'-di-tert.butyl-oxanilid, 2-Ethoxy-2'-ethyl-oxanilid, N,N'-Bis-(3-dimethylaminopropyl)-oxalamid, 2-Ethoxy-5-tert.butyl-2'-ethyl- oxanilid und dessen Gemisch mit 2-Ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilid, Gemische von ortho-und para-Methoxy- sowie von o- und p-Ethoxy-di-substituierte Oxaniliden.2.7. Oxalic acid diamides such as 4,4'-di-octyloxy-oxanilide, 2,2'-di-octyloxy-5,5'-di-tert.butyl-oxanilide, 2,2'-di-dodecyloxy-5,5 ' -di-tert.butyl-oxanilide, 2-ethoxy-2'-ethyl-oxanilide, N, N'-bis- (3-dimethylaminopropyl) -oxalamide, 2-ethoxy-5-tert.butyl-2'-ethyl- oxanilide and its mixture with 2-ethoxy-2'-ethyl-5,4'-di-tert.butyl-oxanilide, mixtures of ortho- and para-methoxy and of o- and p-ethoxy-di-substituted oxanilides.

3. Metalldesaktivatoren, wie z.B. N,N'-Diphenyloxalsäurediamid, N-Salicylal-N'-salicyloylhydrazin, N,N'-Bis-salicyloylhydrazin, N,N'-Bis-(3,S-di-tert.butyl-4-hydroxyphenylpropionyl)-hydrazin, 3-Salicyloylamino-1,2,4-triazol, Bis-benzyliden-oxalsäuredihydrazid.3. Metal deactivators, e.g. N, N'-diphenyloxalic acid diamide, N-salicylal-N'-salicyloyl hydrazine, N, N'-bis-salicyloyl hydrazine, N, N'-bis (3, S-di-tert.butyl-4-hydroxyphenylpropionyl) hydrazine, 3-salicyloylamino-1,2,4-triazole, bis-benzylidene-oxalic acid dihydrazide.

4. Phosphite und Phosphonite, wie z.B. Triphenylphosphit, Diphenylalkylphosphite, Phenyldialkylphosphite, Tri-(nonylphenyl)-phosphit, Trilaurylphosphit, Trioctadecylphosphit, Distearyl-pentaerythritdiphosphit, Tris-(2,4-di-tert.butylphenyl)-phosphit, Diisodecylpentaerythrit-diphosphit, Di-(2,4-di-tert.butylphenyl)-pentaerythritdi- phosphit, Tristearyl-sorbit-triphosphit, Tetrakis-(2,4-di-tert.butylphenyl)-4,4'-biphenylen-diphosphonit.4. Phosphites and phosphonites, e.g. Triphenyl phosphite, diphenylalkyl phosphite, phenyl dialkyl phosphite, tri- (nonylphenyl) phosphite, trilauryl phosphite, trioctadecyl phosphite, distearyl-pentaerythritol diphosphite, tris- (2,4-di-tert.butylphenyl) phosphite, diisodhritol-diisodhritol-di -tert.butylphenyl) pentaerythritol diphosphite, tristearyl sorbitol triphosphite, tetrakis (2,4-di-tert.butylphenyl) -4,4'-biphenylene diphosphonite.

5. Peroxidzerstörende Verbindungen, wie z.B. Ester der ß-Thio-dipropionsäure, beispielsweise der Lauryl-, Stearyl-, Myristyl- oder Tridecylester, Mercaptobenzimidazol, das Zinksalz des 2-Mercaptobenzimidazols, Zink-dibutyl-dithiocarbamat, Dioctadecyldisulfid, Pentaerythrit-tetrakis-(ß-dodecylmercapto)-propionat.5. Peroxide destroying compounds, e.g. Esters of ß-thio-dipropionic acid, for example lauryl, stearyl, myristyl or tridecyl esters, mercaptobenzimidazole, the zinc salt of 2-mercaptobenzimidazole, zinc dibutyl dithiocarbamate, dioctadecyl disulfide, pentaerythritol tetrakod (d) tetrakis (δ).

6. Polyamidstabilisatoren, wie z.B. Kupfersalze in Kombination mit Jodiden und/oder Phosphorverbindungen und Salze des zweiwertigen Mangans.6. Polyamide stabilizers, e.g. Copper salts in combination with iodides and / or phosphorus compounds and salts of divalent manganese.

7. Basische Co-Stabilisatoren, wie z.B. Melamin, Polyvinylpyrrolidon, Dicyandiamid, Triallylcyanurat, Harnstoff-Derivate, Hydrazin-Derivate, Amine, Polyamide, Polyurethane, Alkali- und Erdalkalisalze höherer Fettsäuren, beispielsweise Ca-Stearat, Zn-Stearat, Mg-Stearat, Na-Ricinoleat, K-Palmitat, Antimonbrenzcatechinat oder Zinnbrenzcatechinat.7. Basic co-stabilizers such as e.g. Melamine, polyvinylpyrrolidone, dicyandiamide, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes, alkali and alkaline earth metal salts of higher fatty acids, for example Ca stearate, Zn stearate, Mg stearate, Na ricinoleate, K palmitate, Antimony catecholate or tin catecholate.

8. Nukleierungsmittel, wie z.B. 4-tert.Butylbenzoesäure, Adipinsäure, Diphenylessigsäure.8. Nucleating agents, e.g. 4-tert-butylbenzoic acid, adipic acid, diphenylacetic acid.

9. Füllstoffe und Verstärkungsmittel, wie z.B. Calciumcarbonat, Silikate, Glasfasern, Asbest, Talk, Kaolin, Glimmer, Bariumsulfat, Metalloxide und -hydroxide, Russ, Graphit.9. Fillers and reinforcing agents such as e.g. Calcium carbonate, silicates, glass fibers, asbestos, talc, kaolin, mica, barium sulfate, metal oxides and hydroxides, carbon black, graphite.

10. Sonstige Zusätze, wie z.B. Weichmacher, Gleitmittel, Emulgatoren, Pigmente, Optische Aufheller, Flammschutzmittel, Antistatika, Treibmittel.10. Other additives, such as Plasticizers, lubricants, emulsifiers, pigments, optical brighteners, flame retardants, antistatic agents, blowing agents.

Die folgenden Beispiele sollen der besseren Veranschaulichung der vorliegenden Erfindung dienen und bedeuten keinerlei Einschränkung der Erfindung.The following examples are provided to better illustrate the present invention and are not intended to limit the invention in any way.

Beispiel 1: 35,1 g (0,1 Mol) 2-[N-(2,2,6,6-Tetramethylpiperidin-4-yl)-butylamino]-4,6-dimethoxy-1,3,5-trizain, 20,1 g (0,1 Mol) 1-(2-Hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol, 0,3 g Natriumhydrid und 200 ml Xylol werden während 12 Stunden unter Rückfluss erhitzt. Das Lösungsmittel wird dabei langsam, zusammen mit dem bei der Umsetzung sich bildenden Methanol, abdestilliert und mit der gleichen Volumenmenge an frischem Lösungsmittel ersetzt. Das Reaktionsgemisch wird zur Trockne abgedampft und der Rückstand gemahlen, mit Wasser gewaschen und getrocknet.Example 1: 35.1 g (0.1 mol) of 2- [N- (2,2,6,6-tetramethylpiperidin-4-yl) butylamino] -4,6-dimethoxy-1,3,5-trizain , 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidin-4-ol, 0.3 g of sodium hydride and 200 ml of xylene are heated under reflux for 12 hours. The solvent is slowly distilled off together with the methanol formed during the reaction and replaced with the same volume of fresh solvent. The reaction mixture is evaporated to dryness and the residue is ground, washed with water and dried.

Man erhält ein Produkt mit Smp. 205-215°C und mittlerem Molekulargewicht Mn 4'300.A product is obtained with mp. 205-215 ° C and average molecular weight Mn 4,300.

Beispiele 2 und 3: Wiederholt man das unter Beispiel 1 beschriebene Verfahren mit den in der nachfolgenden Tabelle auch mengenmässig angegebenen Edukten, so erhält man entsprechende Verbindungen der Formel I

Figure imgb0011
Figure imgb0012
 Examples 2 and 3: If the process described in Example 1 is repeated with the starting materials also given in quantitative terms in the table below, corresponding compounds of the formula I are obtained
Figure imgb0011
Figure imgb0012

Beispiel 4: 26,8 g (0,1 Mol) 4-0ctylamino-2,2,6,6-Tetramethylpiperidin werden langsam einer auf O°C abgekühlten Lösung von 18,5 g (0,1 Mol) Cyanurchlorid in 180 ml Trimethylbenzol zugegeben, wobei die Temperatur 10°C nicht übersteigen darf. Danach wird bei der gleichen Temperatur eine Lösung von 4 g Natriumhydrid in 50 ml Wasser zugesetzt. Dem so erhaltenen Gemisch werden 20,1 g (0,1 Mol) 1-(2-Hydroxyethyl)-2,2,6,6-tetramethylpiperidin-4-ol und 12 g Natriumhydroxid beigefügt. Das Gemisch wird 20 Stunden unter Rückfluss gekocht und das Wasser azeotrop entfernt.Example 4: 26.8 g (0.1 mol) of 4-0ctylamino-2,2,6,6-tetramethylpiperidine slowly become a solution of 18.5 g (0.1 mol) of cyanuric chloride in 180 ml cooled to 0 ° C. Trimethylbenzene added, the temperature must not exceed 10 ° C. A solution of 4 g of sodium hydride in 50 ml of water is then added at the same temperature. 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidin-4-ol and 12 g of sodium hydroxide are added to the mixture thus obtained. The mixture is refluxed for 20 hours and the water is removed azeotropically.

Nach dem Filtrieren, zwecks Abtrennung der anorganischen Produkte, und nach dem Abdestillieren des Lösungsmittels erhält man ein Produkt mit Smp. 145-152°C und mittlerem Molekulargewicht Mn 2'200.After filtering, in order to separate off the inorganic products, and after distilling off the solvent, a product is obtained with mp. 145-152 ° C. and average molecular weight Mn 2,200.

Beispiele 5 und 6: Wiederholt man das unter Beispiel 4 beschriebene Verfahren mit den in der nachfolgenden Tabelle auch mengenmässig angegebenen Edukten, so erhält man entsprechende Verbindungen der Formel I.

Figure imgb0013
Examples 5 and 6: If the process described in Example 4 is repeated with the starting materials also given in quantitative terms in the table below, corresponding compounds of the formula I are obtained.
Figure imgb0013

Beispiel 7: 20,4 g (0,05 Mol) 2,4-Dimethoxy-6-[N-(2,2,6,6-Tetramethyl-piperdin-4-yl)-octylamino]-1,3,5-triazin, 20,1 g (0,1 Mol) 1-(2-Hydroxyethyl)-2,2,6,6-Tetramethylpiperidin-4-ol, 0,25 g Natrium und 200 ml Xylol werden 8 Stunden unter Rückfluss gekocht. Das Lösungsmittel wird dabei langsam, zusammen mit dem bei der Umsetzung sich bildenden Methanol, abdestilliert und mit der gleichen Volumenmenge an frischem Lösungsmittel ersetzt.Example 7: 20.4 g (0.05 mol) of 2,4-dimethoxy-6- [N- (2,2,6,6-tetramethyl-piperdin-4-yl) octylamino] -1,3,5 triazine, 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethylpiperidin-4-ol, 0.25 g of sodium and 200 ml of xylene are boiled under reflux for 8 hours . The solvent is slowly distilled off together with the methanol formed during the reaction and replaced with the same volume of fresh solvent.

Das Gemisch wird auf 80°C abgekühlt, dann werden 7,3 g (0,05 Mol) Dimethylsuccinat zugefügt und weitere 8 Stunden am Rückfluss gekocht, bei fortdauerndem Ersatz des Lösungsmittels.The mixture is cooled to 80 ° C., then 7.3 g (0.05 mol) of dimethyl succinate are added and the mixture is refluxed for a further 8 hours, with continued replacement of the solvent.

Nach Reaktionsende wird das Gemisch mit 200 ml Xylol verdünnt, filtriert und das Filtrat zur Trockne eingedampft. Das erhaltene Produkt schmilzt bei 95-103°C und hat ein mittleres Molekulargewicht Mn von 3'700.After the reaction has ended, the mixture is diluted with 200 ml of xylene, filtered and the filtrate is evaporated to dryness. The product obtained melts at 95-103 ° C and has an average molecular weight Mn of 3,700.

Beispiel 8: Wiederholt man das in Beispiel 7 beschriebene Verfahren mit 17,55 g (0,05 Mol) 2-[N-(2,2,6,6-Tetramethyl-piperidin-4-yl)-butylamino]-4,6-dimethoxy-1,3,5-triazin, 20,1 g (0,1 Mol) 1-(2-Hydroxyethyl)-2,2,6,6-Tetramethyl-piperidin-4-ol und 7,3 g (0,05 Mol) Dimethylsuccinat als Ausgangsprodukte, so erhält man ein Produkt mit Smp. 125-134°C und mittlerem Molekulargewicht Mn 2'000.Example 8: Repeating the procedure described in Example 7 with 17.55 g (0.05 mol) of 2- [N- (2,2,6,6-tetramethyl-piperidin-4-yl) butylamino] -4, 6-dimethoxy-1,3,5-triazine, 20.1 g (0.1 mol) of 1- (2-hydroxyethyl) -2,2,6,6-tetramethyl-piperidin-4-ol and 7.3 g (0.05 mol) of dimethyl succinate as starting products, a product is obtained with mp. 125-134 ° C. and average molecular weight Mn 2,000.

Beispiel 9: Je 2 g der in Tabelle 1 angeführten Verbindungen und 1 g Pentaerythrit-tetrakis-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionat (Antioxidans) werden mit 1000 g Polypropylen mit einem Schmelzindex von 2,4 (®Propathen HF 18, Produkt der Imperial Chemical Industries) und 1 g Calciumstearat innig vermischt.Example 9: 2 g each of the compounds listed in Table 1 and 1 g of pentaerythritol tetrakis-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (antioxidant) are mixed with 1000 g of polypropylene with a melt index of 2.4 (®Propathen HF 18, product of Imperial Chemical Industries) and 1 g calcium stearate intimately mixed.

Das erhaltene Gemisch wird dann bei einer Temperatur von 180 bis 220°C extrudiert und zu Granulat verarbeitet, aus dem man Bänder einer Dicke von 50 um und einer Breite von 2,5 mm herstellt. Die Arbeitsbedingungen sind:

  • Extrudertemperatur : 220 bis 240°C
  • Kopftemperatur : 240°CV
  • Streckverhältnis : 1:6

die erhaltenen Bänder werden auf weisser Pappe angeordnet in einem Weather-Ometer.65 WR(ASTM G 27-70) bei einer Temperatur der schwarzen Tafel von 63°C ausgesetzt. Von Zeit zu Zeit werden Proben entnommen, an denen man die verbleibende Zugfestigkeit mittels eines Tensometers mit konstanter Geschwindigkeit misst; danach bestimmt man die zum Halbieren der ursprünglichen Zugfestigkeit erforderliche Aussetzungszeit (T50).The mixture obtained is then extruded at a temperature of 180 to 220 ° C. and processed into granules, from which strips with a thickness of 50 μm and a width of 2.5 mm are produced. The working conditions are:
  • Extruder temperature: 220 to 240 ° C
  • Head temperature: 240 ° CV
  • Stretch ratio: 1: 6

the tapes obtained are arranged on white cardboard in a weather ometer . 65 WR (ASTM G 27-70) exposed at a black board temperature of 63 ° C. From time to time, samples are taken on which the remaining tensile strength is measured at constant speed using a tensometer; then determining the time required to halve the initial tensile strength A u ssetzungsze it (T 50).

Die Resultate sind in Tabelle 1 wiedergegeben.

Figure imgb0014
The results are shown in Table 1.
Figure imgb0014

Beispiel 10: Je 2,5 g der in Tabelle 2 angeführten Verbindungen und 1 g n-Octadecyl-3-(3,5-di-t-butyl-4-hydroxyphenyl)-propionat (Antioxidans) werden mit 1000 g Polypropylen mit einem Schmelzindex von 13 (®Propathen HF 85, Produkt der Imperial Chemical Industries), 1 g Calciumstearat und 2,5 g Titandioxid (®KRONOS RN 57) innig vermischt.Example 10: 2.5 g each of the compounds listed in Table 2 and 1 g of n-octadecyl-3- (3,5-di-t-butyl-4-hydroxyphenyl) propionate (antioxidant) are mixed with 1000 g of polypropylene with a Melt index of 13 (®Propathen HF 85, product of Imperial Chemical Industries), 1 g calcium stearate and 2.5 g titanium dioxide (®KRONOS RN 57) intimately mixed.

Das erhaltene Gemisch wird dann bei einer Temperatur von 180 bis 220°C extrudiert und zu Granulat verarbeitet. Die so erhaltenen Granulate werden unter folgenden Bedingungen zu Fasern (Titer:

  • 20 den/Faser) verarbeitet:
  • Extrudertemperatur : 220 bis 240°C
  • Kopftemperatur : 240°C
  • Streckverhältnis : 1:3,5
The mixture obtained is then extruded at a temperature of 180 to 220 ° C and processed into granules. The granules thus obtained become fibers under the following conditions (titer:
  • 20 den / fiber) processed:
  • Extruder temperature: 220 to 240 ° C
  • Head temperature: 240 ° C
  • Stretch ratio: 1: 3.5

Die erhaltenen Fasern werden auf weisser Pappe angeordnet in einem Weather-Ometer.65 WR bei einer Temperatur der schwarzen Tafel von 63°C ausgesetzt. Der T50-Wert wird wie unter Beispiel 9 beschrieben bestimmt.The fibers obtained are placed on white cardboard in a Weather-Ometer.65 WR at a black board temperature of 63 ° C. The T 50 value is determined as described in Example 9.

Die Resultate sind in Tabelle 2 wiedergegeben.

Figure imgb0015
The results are shown in Table 2.
Figure imgb0015

Claims (6)

1. Verbindungen der Formel I
Figure imgb0016
worin R1 und R2 unabhängig voneinander Wasserstoff, C1-C18 Alkyl, durch Hydroxy, C1-C18 Alkoxy oder C2-C18 Dialkylamino substituiertes C2-C12 Alkyl, C 3-C 18 Alkenyl, C 5-C 18 Cycloalkyl, C6-C18 Aryl, C7-C18 Aralkyl oder eine Gruppe der Formel II
Figure imgb0017
bedeuten, worin R6 Wasserstoff, C1-C12 Alkyl, C3-C12 Alkenyl oder Alkynyl, C7-C12 Aralkyl oder C1-C12 Acyl ist, oder R1 und R2 zusammen mit dem Stickstoffatom an dem sie gebunden sind einen heterocyclischen Rest ausgewählt aus der Gruppe bestehend aus Pyrrolidin-1-yl, Piperidin-1-yl, Hexahydroazepin-1-yl, Morpholin-4-yl und 4-Methylpiperazin-1-yl bilden, R3 und R5 unabhängig voneinander eine der Gruppen der Formeln III, IV, V oder VI
Figure imgb0018
bedeuten und R5 zusätzlich eine Gruppe der Formel VII
Figure imgb0019
sein kann, worin R7 Wasserstoff, C1-C6 Alkyl oder Phenyl ist, X eine Gruppe -O-(CH2)n-O- oder -N(R8)-C(O)-(CH2)n-C(O)-N(R8)- bedeutet, n eine Zahl von 1 bis 6 ist, R8 die gleiche Bedeutung wie R1 und R2 hat und Y C2-C12 Alkylen, durch eine Hydroxygruppe substituiertes oder durch ein Sauerstoffatom unterbrochenes C3-C12 Alkylen, C 4-C 12 Alkenylen oder C8-C12 Aralkylen bedeutet, R4 C2-C18 Diacyl oder eine Gruppe der Formel VIII
Figure imgb0020
ist, worin R1 und R2 die oben angegebene Bedeutung haben, a eine Zahl zwischen 0,2 und 1 und b eine Zahl zwischen Null und 0,8 sind, wobei die Verbindungen der Formel I ein mittleres Molekulargewicht Mn zwischen 1'000 und 20'000 aufweisen.1. Compounds of formula I.
Figure imgb0016
 wherein R 1 and R 2 independently of one another are hydrogen, C 1 -C 18 alkyl, C 2 -C 12 alkyl substituted by hydroxy, C 1 -C 18 alkoxy or C 2 -C 18 dialkylamino, C 3 - C 18 alkenyl, C 5 - C 18 cycloalkyl, C 6 -C 18 aryl, C 7 -C 18 aralkyl or a group of formula II
Figure imgb0017
 mean, wherein R 6 is hydrogen, C 1 -C 12 alkyl, C 3 -C 12 alkenyl or alkynyl, C 7 -C 12 aralkyl or C 1 -C 12 acyl, or R 1 and R 2 together with the nitrogen atom on the they are bonded to form a heterocyclic radical selected from the group consisting of pyrrolidin-1-yl, piperidin-1-yl, hexahydroazepin-1-yl, morpholin-4-yl and 4-methylpiperazin-1-yl, R 3 and R 5 independently of one another one of the groups of the formulas III, IV, V or VI
Figure imgb0018
 mean and R 5 additionally represents a group of formula VII
Figure imgb0019
 where R 7 is hydrogen, C 1 -C 6 alkyl or phenyl, X is a group -O- (CH 2 ) nO- or -N (R 8 ) -C (O) - (CH 2 ) n -C (O) -N (R 8 ) - means n is a number from 1 to 6, R 8 has the same meaning as R 1 and R 2 and YC 2 -C 12 alkylene, substituted by a hydroxyl group or interrupted by an oxygen atom, C 3 -C 12 alkylene, C 4 - C 12 alkenylene or C 8 -C 12 aralkylene, R 4 C 2 -C 18 diacyl or a group of the formula VIII
Figure imgb0020
 in which R 1 and R 2 have the meaning given above, a is a number between 0.2 and 1 and b is a number between zero and 0.8, the compounds of the formula I having an average molecular weight Mn between 1,000 and Have 20,000. 2. Verbindungen gemäss Anspruch 1, der Formel I, worin R1 und R2 unabhängig voneinander Wasserstoff, C1-C12 Alkyl, durch C1-C12 Alkoxy substituiertes C2-C6 Alkyl, C3-C6 Alkenyl, C6-C10 Cycloalkyl oder eine Gruppe der Formel II bedeuten, worin R6 Wasserstoff, Methyl, Allyl, Benzyl oder Acetyl ist, oder R1 und R2 zusammen mit dem Stickstoffatom an dem sie gebunden sind Pyrrolidin-1-yl, Piperidin-1-yl, Hexahydroazepin-1-yl oder Morpholin-4-yl bilden, R3 und R5 eine Gruppe der Formel III sind und R5 zusätzlich eine Gruppe der Formel VII sein kann, R7 Wasserstoff, Methyl oder Ethyl ist, Y C2-C6 Alkylen, But-2-en-1,4-diyl oder Xylylen bedeutet, R4 C2-C12 Diacyl oder eine Gruppe der Formel VIII ist, worin R1 und R2 die oben angegebene Bedeutung haben, a eine Zahl zwischen 0,3 und 1 und b eine Zahl zwischen Null und 0,7 bedeuten, wobei die Verbindungen der Formel I ein mittleres Molekulargewicht Mn zwischen 1'500 und 10'000 aufweisen.2. Compounds according to claim 1, of formula I, in which R 1 and R 2 independently of one another are hydrogen, C 1 -C 12 alkyl, C 2 -C 6 alkyl substituted by C 1 -C 12 alkoxy, C 3 -C 6 alkenyl, C 6 -C 10 cycloalkyl or a group of the formula II in which R 6 is hydrogen, methyl, allyl, benzyl or acetyl, or R 1 and R 2 together with the nitrogen atom to which they are attached pyrrolidin-1-yl, piperidine Form -1-yl, hexahydroazepin-1-yl or morpholin-4-yl, R 3 and R 5 are a group of the formula III and R 5 can additionally be a group of the formula VII, R 7 is hydrogen, methyl or ethyl, YC 2 -C 6 alkylene, but-2-en-1,4-diyl or xylylene, R 4 is C 2 -C 12 diacyl or a group of the formula VIII, in which R 1 and R 2 have the meaning given above, a is a number between 0.3 and 1 and b is a number between zero and 0.7, the compounds of the formula I having an average molecular weight Mn between 1,500 and 10,000. 3. Verbindungen gemäss Anspruch 1, der Formel I, worin R1 und R2 unabhängig voneinander C1-C8 Alkyl, Cyclohexyl, 2,2,6,6-Tetramethylpiperidin-4-yl oder 1,2,2,6,6-Pentamethylpiperidin-4-yl bedeuten, R3 und R eine Gruppe der Formel III sind und R5 zusätzlich eine Gruppe der Formel VII sein kann, R7 Wasserstoff oder Methyl ist, Y But-2-en-l,4-diyl oder Xylylen bedeutet, a die Zahl 1 und b Null bedeuten, wobei die Verbindungen der Formel I ein mittleres Molekulargewicht Mn zwischen 1'500 und 6'000 aufweisen.3. Compounds according to claim 1, of formula I, wherein R 1 and R 2 independently of one another are C 1 -C 8 alkyl, cyclohexyl, 2,2,6,6-tetramethylpiperidin-4-yl or 1,2,2,6, 6-pentamethylpiperidin-4-yl mean, R 3 and R are a group of formula III and R 5 can additionally be a group of formula VII, R 7 is hydrogen or methyl, Y is but-2-en-l, 4-diyl or xylylene, a is the number 1 and b denote zero, the compounds of the formula I having an average molecular weight Mn between 1,500 and 6,000. 4. Polymerzusammensetzungen, dadurch gekennzeichnet, dass sie einen synthetischen Polymeren und eine Stabilisatorverbindung der Formel I gemäss Anspruch 1 in einer Menge zwischen 0,01 und 5 Gew.-%, bezogen auf das Gewicht des synthetischen Polymeren, enthalten.4. Polymer compositions, characterized in that they contain a synthetic polymer and a stabilizer compound of formula I according to claim 1 in an amount between 0.01 and 5 wt .-%, based on the weight of the synthetic polymer. 5. Zusammensetzungen nach Anspruch 4, dadurch gekennzeichnet, dass sie zusätzlich zu dem neuen Stabilisator weitere übliche Zusatzstoffe für synthetische Polymere enthalten.5. Compositions according to claim 4, characterized in that they contain, in addition to the new stabilizer, further conventional additives for synthetic polymers. 6. Zusammensetzungen nach Anspruch 4, dadurch gekennzeichnet, dass als synthetisches Polymer Polyäthylen oder Polypropylen vorliegt.6. Compositions according to claim 4, characterized in that the synthetic polymer is polyethylene or polypropylene.
EP84810455A 1983-09-23 1984-09-17 Polymer compounds containing piperidyl groups and their use as stabilisers in synthetic polymers Expired EP0142467B1 (en)

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